CN111370667A - Three-dimensional ordered porous sulfur-carrying material for positive pole piece of lithium-sulfur battery and preparation method and application thereof - Google Patents
Three-dimensional ordered porous sulfur-carrying material for positive pole piece of lithium-sulfur battery and preparation method and application thereof Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 9
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 9
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000004793 Polystyrene Substances 0.000 claims description 24
- 229920002223 polystyrene Polymers 0.000 claims description 24
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000006256 anode slurry Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- WBVDQFAPFUMTFF-UHFFFAOYSA-N [C].[N].[Co] Chemical compound [C].[N].[Co] WBVDQFAPFUMTFF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 15
- 239000005077 polysulfide Substances 0.000 abstract description 15
- 150000008117 polysulfides Polymers 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 238000003487 electrochemical reaction Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 4
- 230000006698 induction Effects 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01—ELECTRIC ELEMENTS
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/624—Electric conductive fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the field of electrochemical energy storage, in particular to a three-dimensional ordered porous sulfur-carrying material for a positive pole piece of a lithium-sulfur battery, and a preparation method and application thereof. The combination of the template method and the solvent induction method leads the anode sulfur-carrying material to be evenly and orderly distributed with macropores, and the ordered macropores are connected by a framework containing abundant micropores and mesoporous structures. In addition, in the porous conductive framework, polar site zinc sulfide and monoatomic active site Co-N-C are widely distributed to fix polysulfide intermediate products generated in the electrochemical reaction process so as to reduce the problem of rapid capacity attenuation caused by the shuttle effect. The three-dimensional ordered porous sulfur-carrying material can ensure that the positive pole piece of the lithium-sulfur battery stably operates under high sulfur content and high current, thereby effectively promoting the possibility of large-scale commercial application of the lithium-sulfur battery and laying a solid foundation for realizing the application of the next generation of high energy density battery to mobile electronic equipment and electric automobiles.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a three-dimensional ordered porous sulfur-carrying material for a positive pole piece of a lithium-sulfur battery, and a preparation method and application thereof.
Background
In recent years, with the rapid development and popularization of various electronic products and electric vehicles, the demand of batteries with high energy density is more and more urgent. However, conventional lithium ion batteries that implement electrochemical energy storage based on a lithium ion intercalation and deintercalation process have approached their energy density limit. In order to develop a new next-generation battery with small volume, light weight and large capacity, new electrode materials and new electrochemical energy storage systems must be developed.
The lithium-sulfur battery takes the metal lithium sheet as the negative electrode and the elemental sulfur as the positive electrode, and the theoretical energy density of the lithium-sulfur battery can reach 2600Wh/kg, which is about 6 times of the energy density which can be reached by the existing lithium ion battery technology. In addition, the sulfur has the advantages of large reserves, low price, no toxicity and no pollution. Therefore, lithium sulfur batteries are considered as one of the most promising candidates for next-generation high energy density batteries.
However, there are still many problems in the practical application of lithium-sulfur batteries: first, the low conductivity of sulfur makes it difficult for electrons to conduct to the sulfur to participate in the electrochemical reaction discharge. Secondly, during the discharge process, polysulfide intermediates with high solubility are generated, and the polysulfide with high solubility can be dissolved in the electrolyte and diffused to the negative electrode to directly react with the negative electrode metal lithium sheet, and the process is called shuttle effect. The shuttle effect causes a rapid capacity fade of the battery, so that the cycle stability of the lithium sulfur battery is very poor. During the discharge of a lithium-sulfur battery, the active substance sulfur undergoes a solid-state transition to a liquid polysulfide and is finally deposited on the surface of the conductive material in the form of solid lithium sulfide. This complex phase transition process can slow the kinetics of the overall electrochemical reaction, rendering the overall lithium sulfur cell incapable of operating at high currents and also leading to a reduction in sulfur utilization.
Therefore, how to efficiently solve the above problems is a key technology for truly realizing commercial application of lithium sulfur batteries.
Disclosure of Invention
The invention aims to provide a three-dimensional ordered porous sulfur-carrying material for a positive pole piece of a lithium-sulfur battery, and a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a three-dimensional ordered porous sulfur-carrying material for a positive pole piece of a lithium-sulfur battery comprises a hierarchical pore structure, namely the material comprises three pore structures of a macropore, a mesopore and a micropore; wherein, the macropores are uniformly and orderly distributed in the conductive carbon frame rich in mesopores and micropores; bipolar adsorption sites consisting of polar adsorption sites, zinc sulfide and monoatomic active sites, cobalt nitrogen carbon, are widely and uniformly distributed in the conductive carbon framework;
in the sulfur-carrying material, the aperture of a large pore is more than 50nm to 180nm and is orderly distributed in a conductive carbon frame, the aperture of a medium pore in the conductive carbon frame is between 2nm and 50nm, and the aperture of a small pore is between 0.1 nm and less than 2 nm.
The preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery comprises the following specific steps:
the method comprises the following steps: preparing reaction liquid from styrene, water and polyvinylpyrrolidone, heating to 70-80 ℃ under the protection of nitrogen, adding potassium persulfate, reacting for 20-30 hours, and performing centrifugal separation to obtain polystyrene nanoparticles;
step two: ultrasonically dispersing the obtained polystyrene nanoparticles in absolute ethyl alcohol, placing the polystyrene nanoparticles in a smooth surface vessel, evaporating the ethyl alcohol at room temperature, and completely evaporating the ethyl alcohol to obtain a three-dimensional polystyrene template;
step three: dissolving zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole in methanol, introducing the prepared solution into the obtained three-dimensional polyethylene template after the zinc nitrate hexahydrate, the cobalt nitrate hexahydrate and the 2-methylimidazole are completely dissolved, and standing for 0.5-2 hours at room temperature;
step four: after standing, taking out the soaked three-dimensional polyethylene template, putting the three-dimensional polyethylene template into a mixed solution of methanol and ammonia water, and standing for 20-30 hours;
step five: after standing, taking out the soaked three-dimensional polyethylene template, putting the three-dimensional polyethylene template into a tetrahydrofuran solvent, and stirring for 20-30 hours;
step six: and after stirring, separating the solution by using a centrifugal machine to obtain a light purple solid sample, naturally airing the obtained solid sample, and carbonizing the solid sample for 1-3 hours under the protection of nitrogen to obtain the three-dimensional ordered porous lithium-sulfur battery sulfur-carrying material containing the bipolar adsorption sites.
In the first step, the mass ratio of styrene to water to polyvinylpyrrolidone to potassium persulfate is 1: 2-10: 0.1-5: 0.1 to 5.
In the third step, the mass ratio of zinc nitrate hexahydrate, cobalt nitrate hexahydrate, 2-methylimidazole and methanol is 1-10: 1: 1-10: 1 to 10.
In the fourth step, the volume ratio of the methanol to the ammonia water is 1: 1.
the preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery comprises the sixth step of carbonizing at 700-1000 ℃.
The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery is characterized in that the three-dimensional ordered porous sulfur-carrying material is mixed with sulfur powder and treated, so that active substance sulfur is stored in a macroporous cavity of the three-dimensional ordered porous sulfur-carrying material, and a carbon-sulfur compound is obtained and used as the positive pole of the lithium-sulfur battery.
The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery is characterized in that the synthesized three-dimensional ordered porous sulfur-carrying material containing bipolar adsorption sites and elemental sulfur powder are mixed according to the weight ratio of 1: 2-4, fully grinding, adding into a closed container under the protection of argon, heating to 150-160 ℃, preserving heat for 12-24 hours, and taking out to obtain the carbon-sulfur compound.
The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery is characterized in that the specific preparation process of the positive pole of the lithium-sulfur battery is as follows:
(1) preparing lithium-sulfur battery positive electrode slurry: mixing a carbon-sulfur compound, a conductive agent and an adhesive according to the ratio of 8-9: 0.1-1: dispersing the mixture in N-methyl pyrrolidone in a mass ratio of 0.1-1, and fully stirring for 4-12 hours to form anode slurry, wherein the solid content in the anode slurry is 40-60 wt%;
(2) uniformly coating the positive electrode slurry prepared in the step (1) on a current collector, fully drying at the temperature of 50-100 ℃ for 12-24 hours, and cutting to obtain a positive electrode piece of the lithium-sulfur battery;
(3) and continuously putting the cut positive pole piece of the lithium-sulfur battery into a vacuum drying oven, and drying for 12-24 hours at 50-100 ℃.
The three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery is applied, the conductive agent is Ketjen black or acetylene black, the adhesive is polyvinylidene fluoride, polyacrylic acid, polyvinyl alcohol, polytetrafluoroethylene or sodium carboxymethylcellulose, and the current collector is one of aluminum foil, carbon paper, carbon cloth, foamed nickel, graphite felt, foamed carbon and electrostatic spinning carbon fiber.
The design idea of the invention is as follows:
the method is the combination of a template method and a solvent induction method, macropores are uniformly and orderly distributed in the prepared anode sulfur-carrying material, and the ordered macropores are connected by a framework containing rich micropores and mesoporous structures. In the porous conductive framework, polar site zinc sulfide (ZnS) and monoatomic active site cobalt nitrogen carbon (Co-N-C) are widely distributed to fix polysulfide intermediate products generated in the electrochemical reaction process so as to reduce the problem of rapid capacity attenuation caused by the shuttle effect.
The macroporous structure is uniformly distributed, and the loading capacity of the active substance sulfur can be effectively improved. Meanwhile, the large pore volume can ensure that the electrolyte can be smoothly conducted in the sulfur-carrying material, and the ion conduction resistance is effectively reduced. In order to solve the problem of polysulfide exudation caused by large pore volume, polar sites ZnS and monoatomic active sites Co-N-C are introduced into a sulfur-carrying material to effectively adsorb polysulfide. Therefore, the sulfur-carrying material can effectively reduce the capacity reduction problem caused by the exudation and dissolution of polysulfide under the condition of extremely large sulfur carrying capacity.
The invention has the following advantages and beneficial effects:
1. the ordered macropores in the three-dimensional ordered porous sulfur-carrying material used in the invention can greatly improve the content of active substance sulfur in the sulfur-carrying material, and the mass fraction of sulfur in the carbon-sulfur composite can reach 80% or higher. Therefore, the actual specific capacity of the positive electrode of the lithium-sulfur battery can be greatly improved. Meanwhile, the large pore volume can also ensure that the electrolyte can circulate in the sulfur-carrying material, thereby greatly reducing the ion transmission resistance and ensuring that the lithium-sulfur battery can stably operate under the heavy-current operation condition.
2. According to the invention, the polar adsorption site zinc sulfide and the monoatomic active site Co-N-C are used as the bipolar adsorption sites, so that the adsorption effect of the sulfur-carrying material on polysulfide dissolved in electrolyte can be greatly improved, the problem of battery capacity attenuation caused by the shuttle effect of the polysulfide is effectively inhibited, and the cycle stability of the lithium-sulfur battery is greatly improved.
3. The reactants and preparation instruments used in the preparation process are simple and easy to obtain and have low price, so that the preparation cost of the whole lithium-sulfur battery anode is low, and the possibility of large-scale production exists, thereby having great promotion effect on large-scale commercial application of the lithium-sulfur battery.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the polystyrene nanoparticles prepared in example 1.
FIG. 2 is a projection electron microscope (TEM) image of the three-dimensional ordered porous sulfur-bearing material prepared in example 1.
Fig. 3 is a charge-discharge curve of the three-dimensional ordered porous sulfur-carrying material prepared in example 2 and the lithium-sulfur battery positive electrode plate prepared from sublimed sulfur under a current of 0.2C.
Fig. 4 is a charge-discharge curve of the three-dimensional ordered porous sulfur-carrying material prepared in example 2 and the lithium-sulfur battery positive electrode plate prepared from sublimed sulfur under a current of 5.0C.
Fig. 5 is a charge-discharge curve of the conductive agent prepared in example 3 and the positive electrode plate of the lithium-sulfur battery prepared by subliming sulfur under a current of 0.2C.
Fig. 6 is a cycle performance curve of the lithium sulfur battery positive electrode plate prepared from the three-dimensional ordered porous sulfur-carrying material and the sublimed sulfur in example 2 and the lithium sulfur battery positive electrode plate prepared from the conductive agent and the sublimed sulfur in example 3 at a current of 1.0C.
Detailed Description
To facilitate an understanding of the invention, a more complete description of the invention will be provided below, and the advantages of the invention will become apparent as the description proceeds. The present invention is not limited to the embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the specific implementation process, the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery and the preparation method thereof are as follows:
(1) a three-dimensional ordered porous sulfur-carrying material is constructed by adopting a solvent induction method, and the sulfur-carrying material contains macropores, mesopores and micropores. Wherein, the macropores are used for storing active substance sulfur, and the micropores and mesopores are used for conducting electrolyte. Meanwhile, the conductive carbon framework is embedded with the bipolar adsorption sites consisting of zinc sulfide and monoatomic active sites, so that polysulfide generated in electrochemical reaction can be effectively adsorbed, and subsequent electrochemical reaction of the polysulfide can be catalyzed, the shuttle effect of the polysulfide can be effectively restrained, the utilization rate of active substance sulfur can be effectively improved, and the overall coulombic efficiency and long-cycle stability of the lithium-sulfur battery can be improved. In the present invention, the conductive carbon frame means: an electrically conductive carbon framework capable of conducting electrons, obtained from an organometallic framework by high-temperature calcination, the meaning of the adsorption sites being: can effectively adsorb polysulfide on the surface sites thereof by chemical bonding or electrostatic attraction.
(2) Treating the synthesized three-dimensional ordered porous sulfur-carrying material and sulfur powder together to obtain a carbon-sulfur compound, and preparing the obtained carbon-sulfur compound into lithium-sulfur battery anode slurry: the prepared carbon-sulfur compound, the conductive agent and the adhesive are mixed according to the mass ratio of 8-9: 0.1-1: dispersing the mixture in N-methyl pyrrolidone with a proper volume in a ratio of 0.1-1 (preferably 8: 1: 1), and fully stirring for 4-12 hours to form positive electrode slurry.
(3) The preparation method of the lithium-sulfur battery positive electrode comprises the following steps: and (3) uniformly coating the positive electrode slurry prepared in the step (2) on a current collector, fully drying at the temperature of 50-100 ℃ for 12-24 hours, and cutting to obtain a positive electrode piece of the lithium-sulfur battery with a proper size. And continuously putting the cut positive pole piece into a vacuum drying oven, and drying for 12-24 hours at 50-100 ℃.
The present invention will be described in further detail below by way of examples and figures.
Example 1:
in this example, the specific preparation process of the three-dimensional ordered porous sulfur-carrying material is as follows:
(1) preparation of polystyrene nanoparticles:
70mL of styrene solution is washed once with 25mL of 10 wt.% sodium hydroxide solution to remove the stabilizer in the styrene solution, and the styrene solution is washed three times with deionized water and collected for later use.
65mL of the styrene solution after washing was added to 500mL of deionized water to obtain a mixed solution. 2.5g of polyvinylpyrrolidone was added to the mixed solution, and after sufficiently stirring and dissolving, nitrogen gas was continuously introduced into the above solution at room temperature for 30min to remove oxygen in the liquid. Then, the solution is heated to 75 ℃ under the protection of nitrogen or argon in a closed manner. After the temperature had stabilized, 50mL of a solution containing 1g of potassium persulfate was added, and the reaction was continued with stirring at 75 ℃ for 24 hours. After the reaction was completed, the solution was centrifuged and dried in an air-blast drying oven at 60 ℃. And after the drying is finished, the obtained white solid powder is the polystyrene nano-particles.
The structure of the polystyrene spheres of this example will be characterized below:
FIG. 1 is a scanning electron microscope image of the prepared polystyrene beads, from which it can be seen that the synthesized polystyrene beads have a uniform size and the diameter of the nanospheres is 180 nm.
(2) Preparing a three-dimensional polystyrene template:
2g of the synthesized polystyrene nanoparticles were dispersed in 20mL of absolute ethanol and formed into a uniform suspension by an ultrasonic instrument. The resulting suspension was then poured into a flat glass petri dish and heated on a 60 ℃ heating table to evaporate the ethanol. And after the ethanol is completely evaporated, obtaining the flaky three-dimensional polystyrene template. And placing the obtained three-dimensional polystyrene template in a vacuum environment, and exhausting gas in the gap inside the template.
(3) Preparation of three-dimensional organometallic framework material:
3.62g of zinc nitrate hexahydrate, 0.9g of cobalt nitrate hexahydrate and 3.75g of 2-methylimidazole were dissolved in 20mL of anhydrous methanol, and the mixture was sufficiently stirred to obtain a mixed solution. Soaking the three-dimensional polystyrene template prepared in the step (2) in the mixed solution for 1 hour. And after soaking, taking out the three-dimensional polystyrene template, and drying in a 60 ℃ drying oven. After drying, soaking the three-dimensional polystyrene template in a solvent with the volume ratio of 1: 1 in the mixed solution of methanol and strong ammonia water, and keeping for 24 hours. After the step is finished, taking out the three-dimensional polystyrene template, and airing the three-dimensional polystyrene template in a room temperature environment. And after completely airing, soaking the three-dimensional polystyrene template into a proper amount of tetrahydrofuran solvent, and stirring and reacting for 24 hours at room temperature. After complete reaction, a light purple solid sample is obtained by centrifugal separation of a centrifugal machine, namely the three-dimensional organic metal frame, and is placed in a 60 ℃ oven for drying and standby.
(4) Preparing a three-dimensional ordered porous sulfur-carrying material:
and (3) putting the three-dimensional organic metal framework material obtained in the step (3) into a tube furnace under the protection of nitrogen or argon for carbonization for 2 hours, wherein the carbonization temperature is 800 ℃. The black solid powder obtained after the step is finished is three-dimensional ordered porous sulfur-carrying material (conductive carbon framework) powder.
The following will characterize the structure of the three-dimensional ordered porous sulfur-bearing material of this example:
FIG. 2 is a projection electron microscope image of the prepared three-dimensional ordered porous sulfur-carrying material, and it can be known from the image that macropores with a pore diameter of more than 50nm to 180nm are uniformly and orderly distributed in the synthesized three-dimensional ordered porous sulfur-carrying material, and the synthesized three-dimensional ordered porous sulfur-carrying material contains mesopores and micropores, wherein the pore diameter of the mesopores is between 2nm and 50nm, and the pore diameter of the micropores is between 0.1 nm and less than 2 nm. The bipolar adsorption sites composed of polar adsorption sites, zinc sulfide and monoatomic active sites, cobalt, nitrogen and carbon are widely and uniformly distributed in the three-dimensional ordered porous sulfur-carrying material.
Example 2:
in this embodiment, the preparation process of the positive electrode plate of the lithium-sulfur battery is as follows:
(1) the preparation method of the carbon-sulfur compound comprises the following steps:
0.1g of the prepared three-dimensionally ordered porous sulfur-bearing material was taken and sufficiently milled with 0.3g of sublimed sulfur in a mortar to obtain uniform powder. The mixed solid powder was placed in a closed container under argon protection, warmed to 155 ℃, and kept at that temperature for 12 hours. And taking out the obtained mixed powder to obtain the carbon-sulfur compound.
(2) The preparation method of the lithium-sulfur battery positive electrode slurry comprises the following steps:
placing 800mg of the carbon-sulfur compound obtained in the step (1) in a glass bottle, adding 100mg of a conductive agent and 100mg of a bonding agent, adding 3 mLN-methyl pyrrolidone, fully stirring for 5 hours and carrying out ultrasonic treatment to obtain uniform suspension, namely the lithium-sulfur battery positive electrode slurry. The conductive agent can be Ketjen black or acetylene black, and the adhesive can be polyvinylidene fluoride, polyacrylic acid, polyvinyl alcohol, polytetrafluoroethylene or sodium carboxymethylcellulose.
(3) The preparation method of the positive pole piece of the lithium-sulfur battery comprises the following steps:
and (3) uniformly coating the positive electrode slurry obtained in the step (2) on a current collector, and heating at 80 ℃ for 12 hours to evaporate the solvent. And then punching and shearing the positive pole piece by using a metal punch according to the size and shape requirements. And (3) drying the obtained positive pole piece in a vacuum drying oven at 60 ℃ for 12 hours to obtain the positive pole piece of the lithium-sulfur battery. The current collector can be aluminum foil, foamed nickel, carbon paper, graphite felt, carbon cloth, foamed carbon and electrostatic spinning fiber.
The properties of the positive electrode sheet prepared from the carbon-sulfur composite of this example will be characterized as follows:
and punching and shearing the positive pole piece into a pole piece with the diameter of 12mm, assembling the pole piece into a CR2016 button cell by taking a lithium metal piece with the thickness of 0.6mm as a negative pole in a glove box under the protection of argon, and carrying out constant-current charge-discharge test at room temperature at 0.2C. As shown in fig. 3, it can be seen that the specific capacity of the positive electrode plate is 1296.35mAh/g under the condition of 0.2C, while the specific discharge capacity of the lithium iron phosphate positive electrode material commonly used in the present lithium ion battery is 140mAh/g under the conditions of 0.2C and room temperature. The specific capacity of the cathode material developed by the invention is far greater than that of the cathode material commonly used by the commercial lithium ion battery at present, and the invention is further proved to have very key significance for developing the next generation of high energy density battery. In addition, we also performed charge and discharge tests on the positive pole piece developed by the invention under a large current, and the assembled CR2016 button cell was charged and discharged under a 5.0C current, and the charge and discharge curves are shown in fig. 4, which shows that the specific capacity of the positive pole material developed by the invention can still reach 684.95mAh/g even under a large current condition. The cycling stability of the positive pole piece of the lithium-sulfur battery prepared by using the three-dimensional ordered porous sulfur-carrying material under 1C is shown in FIG. 6. The test can prove that the assembled lithium-sulfur battery can run under high current by using the cathode material, so that the working environment of the lithium-sulfur battery is enriched, and a solid foundation is laid for future large-scale commercial application.
Example 3:
in this embodiment, an electrochemical test using a carbon-sulfur compound obtained by directly mixing sublimed sulfur with a conductive agent as a positive electrode sheet includes the following steps:
(1) preparation of carbon-sulfur composite
100mg of Ketjen black and 350mg of sublimed sulfur are put into a mortar, fully ground and then added into a closed container protected by argon. The vessel was heated to 155 ℃ and maintained at that temperature for 12 hours to obtain a carbon-sulfur complex of ketjen black and sublimed sulfur.
(2) Preparation of lithium-sulfur battery positive electrode slurry
And (2) putting 800mg of the carbon-sulfur compound obtained in the step (1) into a glass bottle, adding 100mg of a conductive agent and 100mg of a bonding agent, adding 3 mLN-methyl pyrrolidone, fully stirring for 5 hours and performing ultrasonic treatment to obtain uniform suspension, namely the lithium-sulfur battery positive electrode slurry. The conductive agent can be Ketjen black or acetylene black, and the adhesive can be polyvinylidene fluoride, polyacrylic acid, polyvinyl alcohol, polytetrafluoroethylene or sodium carboxymethylcellulose.
(3) The preparation method of the positive pole piece of the lithium-sulfur battery comprises the following steps:
and (3) uniformly coating the positive electrode slurry obtained in the step (2) on a current collector, and heating and evaporating the solvent at 80 ℃. And then punching and shearing the positive pole piece by using a metal punch according to the size and shape requirements. And (3) drying the obtained positive pole piece in a vacuum drying oven at 60 ℃ for 12 hours to obtain the positive pole piece of the lithium-sulfur battery. Wherein, the current collector can be selected from one of aluminum foil, carbon paper, carbon cloth, foamed nickel, graphite felt, foamed carbon or electrostatic spinning carbon fiber.
The properties of the positive electrode sheet prepared from the carbon-sulfur composite of this example will be characterized as follows:
and punching and shearing the positive pole piece into a pole piece with the diameter of 12mm, assembling the pole piece into a CR2016 button cell by taking a lithium metal piece with the thickness of 0.6mm as a negative pole in a glove box under the protection of argon, and carrying out constant-current charge-discharge test at room temperature at 0.2C. The test result is shown in fig. 5, and it can be seen from the figure that the positive electrode plate of the lithium-sulfur battery prepared by mixing the sublimed sulfur and the conductive agent operates at a current of 0.2C, and the specific capacity of the positive electrode is only 1005mAh/g, which is far lower than the specific capacity of the positive electrode of the lithium-sulfur battery prepared from the three-dimensional ordered porous sulfur-carrying material and the sublimed sulfur. Meanwhile, the cycle performance of the lithium-sulfur battery anode prepared by using the conductive agent and the sublimed sulfur under the current of 1C is shown in FIG. 6, and it can be seen that the cycle stability of the lithium-sulfur battery anode prepared by using the three-dimensional ordered porous sulfur-carrying material and the sublimed sulfur is far better than that of the lithium-sulfur battery anode prepared by directly mixing the conductive agent and the sublimed sulfur. Compared with the prior art, the three-dimensional ordered porous sulfur-carrying material is proved to be capable of improving the utilization efficiency of the anode of the lithium sulfur battery to active substance sulfur, effectively inhibiting the shuttle effect of polysulfide ions and greatly prolonging the cycle life of the whole battery.
The embodiment result shows that the three-dimensional ordered porous sulfur-carrying material can ensure that the positive pole piece of the lithium-sulfur battery stably operates under high sulfur content (80 wt%) and high current (5.0C), thereby effectively promoting the possibility of large-scale commercial application of the lithium-sulfur battery and laying a solid foundation for realizing the application of the next generation of high energy density battery to mobile electronic equipment and electric automobiles.
Claims (10)
1. A three-dimensional ordered porous sulfur-carrying material for a positive pole piece of a lithium-sulfur battery is characterized in that the three-dimensional ordered porous sulfur-carrying material comprises a multi-level pore structure, namely the material comprises three pore structures of a large pore, a medium pore and a small pore; wherein, the macropores are uniformly and orderly distributed in the conductive carbon frame rich in mesopores and micropores; bipolar adsorption sites consisting of polar adsorption sites, zinc sulfide and monoatomic active sites, cobalt nitrogen carbon, are widely and uniformly distributed in the conductive carbon framework;
in the sulfur-carrying material, the aperture of a large pore is more than 50nm to 180nm and is orderly distributed in a conductive carbon frame, the aperture of a medium pore in the conductive carbon frame is between 2nm and 50nm, and the aperture of a small pore is between 0.1 nm and less than 2 nm.
2. The preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery according to claim 1, is characterized by comprising the following specific steps of:
the method comprises the following steps: preparing reaction liquid from styrene, water and polyvinylpyrrolidone, heating to 70-80 ℃ under the protection of nitrogen, adding potassium persulfate, reacting for 20-30 hours, and performing centrifugal separation to obtain polystyrene nanoparticles;
step two: ultrasonically dispersing the obtained polystyrene nanoparticles in absolute ethyl alcohol, placing the polystyrene nanoparticles in a smooth surface vessel, evaporating the ethyl alcohol at room temperature, and completely evaporating the ethyl alcohol to obtain a three-dimensional polystyrene template;
step three: dissolving zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole in methanol, introducing the prepared solution into the obtained three-dimensional polyethylene template after the zinc nitrate hexahydrate, the cobalt nitrate hexahydrate and the 2-methylimidazole are completely dissolved, and standing for 0.5-2 hours at room temperature;
step four: after standing, taking out the soaked three-dimensional polyethylene template, putting the three-dimensional polyethylene template into a mixed solution of methanol and ammonia water, and standing for 20-30 hours;
step five: after standing, taking out the soaked three-dimensional polyethylene template, putting the three-dimensional polyethylene template into a tetrahydrofuran solvent, and stirring for 20-30 hours;
step six: and after stirring, separating the solution by using a centrifugal machine to obtain a light purple solid sample, naturally airing the obtained solid sample, and carbonizing the solid sample for 1-3 hours under the protection of nitrogen to obtain the three-dimensional ordered porous lithium-sulfur battery sulfur-carrying material containing the bipolar adsorption sites.
3. The preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 2, wherein in the step one, the mass ratio of styrene to water to polyvinylpyrrolidone to potassium persulfate is 1: 2-10: 0.1-5: 0.1 to 5.
4. The preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 2, wherein in the third step, the mass ratio of zinc nitrate hexahydrate, cobalt nitrate hexahydrate, 2-methylimidazole and methanol is 1-10: 1: 1-10: 1 to 10.
5. The preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery according to claim 2, wherein in the fourth step, the volume ratio of methanol to ammonia water is 1: 1.
6. the preparation method of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 2, wherein in the sixth step, the carbonization temperature is 700-1000 ℃.
7. The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 1, wherein the three-dimensional ordered porous sulfur-carrying material is mixed with sulfur powder and treated, so that active substance sulfur is stored in a macroporous cavity of the three-dimensional ordered porous sulfur-carrying material, and then the carbon-sulfur composite is obtained to be used as the positive pole of the lithium-sulfur battery.
8. The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 7, characterized in that the synthesized three-dimensional ordered porous sulfur-carrying material containing bipolar adsorption sites and elemental sulfur powder are mixed according to the ratio of 1: 2-4, fully grinding, adding into a closed container under the protection of argon, heating to 150-160 ℃, preserving heat for 12-24 hours, and taking out to obtain the carbon-sulfur compound.
9. The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 7 or 8, wherein the specific preparation process of the positive pole of the lithium-sulfur battery is as follows:
(1) preparing lithium-sulfur battery positive electrode slurry: mixing a carbon-sulfur compound, a conductive agent and an adhesive according to the ratio of 8-9: 0.1-1: dispersing the mixture in N-methyl pyrrolidone in a mass ratio of 0.1-1, and fully stirring for 4-12 hours to form anode slurry, wherein the solid content in the anode slurry is 40-60 wt%;
(2) uniformly coating the positive electrode slurry prepared in the step (1) on a current collector, fully drying at the temperature of 50-100 ℃ for 12-24 hours, and cutting to obtain a positive electrode piece of the lithium-sulfur battery;
(3) and continuously putting the cut positive pole piece of the lithium-sulfur battery into a vacuum drying oven, and drying for 12-24 hours at 50-100 ℃.
10. The application of the three-dimensional ordered porous sulfur-carrying material for the positive pole piece of the lithium-sulfur battery as claimed in claim 9, wherein the conductive agent is ketjen black or acetylene black, the adhesive is polyvinylidene fluoride, polyacrylic acid, polyvinyl alcohol, polytetrafluoroethylene or sodium carboxymethylcellulose, and the current collector is one of aluminum foil, carbon paper, carbon cloth, foamed nickel, graphite felt, foamed carbon and electrospun carbon fiber.
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